Electromagnetic heating of cnt and cnt based derivatives dispersions and solutions or cnt and cnt based derivatives containing coatings or metals for oil and gas equipment for remediation or prevention of solids formation in wellbores

ABSTRACT

A method for heating/removing and/or preventing solids in onshore or subsea pipe or wellbore tubular includes pumping a solution or suspension containing carbon nanotubes (CNT) and/or CNT based derivatives into the pipe or wellbore to a position proximate the solids and applying electromagnetic energy or electric current at one or more selected frequencies to the pipe proximate the solution. The pipe or wellbore tubular itself may be pre-coated with carbon nanotube containing material and exposed to radio frequency energy, microwaves, and electric current upon formation of solids therein.

CROSS-REFERENCE TO RELATED APPLICATIONS

Priority is claimed from U.S. Provisional Application No. 61/679,823 filed on Aug. 6, 2012 and U.S. Provisional Application No. 61/705,357 filed on Sep. 25, 2012 both of which applications are incorporated herein by reference for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

This disclosure relates generally to the field of fusible solids removal from pipes used to produce hydrocarbons from subsurface reservoirs. More specifically, the invention relates to compositions of materials and methods of activating such materials to facilitate removal of heat sensitive solids containing hydrates, wax, paraffins, asphaltenes etc

Thermodynamic conditions favoring solids formation, e.g., hydrate formation, are often found in pipelines. This is highly undesirable because the clathrate crystals might agglomerate and plug the pipeline or flowline and cause flow assurance failure and damage valves and instrumentation. The results can range from flow reduction to equipment damage. Hydrates may be formed in deepwater applications specifically in a tieback (a line that connects a producing well having a sea floor disposed outlet to a central collection and/or processing facility). Currently, to remove a hydrate plug, pressure reductions/pumping methanol is attempted to dissolve the plug, however such method has only shown limited success. Other known techniques include heating a solution of salts on the surface and pumping them down the line, but in long tiebacks the solutions cools too quickly and cannot be reheated. There is currently no known convenient way to heat up such lines and heat/melt/remove the hydrates once a hydrate plug is formed.

Similarly, solids such as asphaltenes, waxes and other paraffins may deposit within tubular components of wellbores during production of hydrocarbons from subsurface reservoirs. Such solids may also be deposited in pipelines if temperature and pressure conditions favor such deposition.

What is needed is a method and system to enable relatively easy removal of solids if and when formed in such subsea or buried onshore lines or wellbores

SUMMARY

One aspect is a method for heating and/or removing and/or preventing fusible solids in a subsea pipe or wellbore which includes pumping a solution or suspension containing carbon nanotubes into the pipe or wellbore to a position proximate the solids and applying electromagnetic energy or electric current at a selected frequency to the pipe or wellbore proximate the solution. The pipe or wellbore tubular itself may be pre-coated or manufactured with carbon nanotubes (CNT) and CNT based derivatives containing material and exposed to radio frequency electromagnetic energy upon formation of solids therein.

Other aspects and advantages will be apparent from the description and claims which follow.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example electromagnetic energy generating instrument in a wellbore.

DETAILED DESCRIPTION

In one example, carbon nanotubes (CNT) and/or CNT based derivatives may be introduced into solutions or liquid suspensions, pumped into a pipe having hydrates and then heating the CNT and/or CNT based derivatives (“collectively “CNT”) in the solution or suspension as needed when the CNT solution or suspension comes into contact with hydrates or surfaces where hydrates adhere, for example, in deepwater flow lines or tiebacks. In some examples, a concentration of the carbon nanotubes and/or CNT based derivatives in the solution or suspension may be in the range of 10 milligrams per liter to 90% by weight.

The solution/suspension of CNT may be pumped into a line with a remotely operated vehicle (ROV) or pre engineered subsea system and heated remotely by applying selected frequency or frequencies electromagnetic energy to the part of the line having the hydrates formed therein. Example solutions may include radio frequency (RF) absorption enhancers (e.g., CNT) added to a salt water solution such as sea water, solutions containing salt water, and salt water mixtures prior to applying electromagnetic energy to enhance the effects of the electromagnetic energy on the salt water, e.g., enhanced heating. The absorption enhancers may be particles made from, for example, RF absorbing materials that absorb one or more frequencies of an electromagnetic signal substantially more than other materials, e.g., the CNT. This may permit the electromagnetic signal to heat salt water (or any solution containing salt water or salt water mixture) containing electromagnetic energy absorbing enhancers, e.g., the CNT, substantially more than it would salt water (or salt water solution or salt water mixture) that does not contain additional electromagnetic energy absorption enhancers.

The electromagnetic energy may be applied, for example, as a 13.56 MHz RF signal, which is expected to be effective to heat RF absorbing carbon molecules and compounds. RF absorption enhancers using these RF absorbing particles are also expected to be effective at slightly higher frequencies, such as those having a frequency on the order of the second or third harmonics of 13.56 MHz. The electromagnetic energy may be applied by having suitable equipment on an ROV, or as will be shown with reference to FIG. 1, on a wireline conveyed instrument within a wellbore casing. The selected frequency is not limited to the foregoing example of 13.56 MHz and may extend into the microwave range, e.g., several GHz or more.

In test experiments, a 250 mg/L suspension of carbon nanotubes in water got as hot as 45° C. within 25 seconds when treated with RF electromagnetic energy.

In other examples, coatings to be applied to the pipe surfaces or added directly to the surface of the metals which form the pipe, CNT could be included in the coatings or bonded to the materials' surface and heated in the same manner. In these cases electric current application may be the more efficient source of EM energy.

In yet other examples, solids consisting of asphaltenes, waxes and/or other paraffins may be deposited in pipelines or wellbore tubular (e.g., casing or production tubing) as a result of producing hydrocarbons from subsurface reservoirs depending on pressure and temperature conditions within the wellbore tubular. The above described method may be used to equal effect on fusing and removal of such solids from wellbore tubulars.

FIG. 1 shows an example electromagnetic energy generating instrument disposed in a wellbore to perform example procedures such as those described hereinabove. The instrument is illustrated generally at 100 during the operation of the instrument 100 in a wellbore 125 drilled through subsurface formations 126.

The instrument 100 may be connected to a wire line 101 which is stored on a wire line truck 102 used to reel in and reel out the wire line 101 as is known. The instrument 100 may be initially positioned within a lubricator 103 on the top of a wellhead 104 and the instrument 100 is lowered on the wire line 101 to the position of interest within a well casing 110. The wire line truck 102 has an associated generator 111 which is connected to a power control unit (PCU) 112 which provides the necessary power to the wire line truck 102 and which, in turn, provides the proper power to the wire line 101 and to the instrument 100. The well casing 110 may include perforations 131 proximate a producing formation and a plug 130 at the bottom thereof.

The instrument 100 may be disposed in a pressure resistant housing 132, and circuits shown generally at 114 may generate electromagnetic energy at the desired frequency to heat the CNTs. Electromagnetic energy may be radiated by transmitter coils 114A in the instrument 100. In other examples, the coils 114A may be substituted by electrodes (also shown at 114) so that electric current at a selected frequency may be passed through the CNTs to heat them in a manner similar to imparting electromagnetic energy.

A pump P may be used to pump mixtures containing CNTs as explained above into the wellbore casing 110 so that areas therein requiring heating may be heated according to the example methods described above.

The example shown in FIG. 1 is only one possible method for conveying an electromagnetic energy generating instrument to places in a pipe or wellbore requiring heating according to the techniques described above. Accordingly, the present disclosure is not limited to wireline conveyance within wellbores, but may extend to any form of conveyance and to any pipe or conduit that may require heating as explained herein.

While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims. 

What is claimed is:
 1. A method for heating and/or removing and/or preventing solids in a pipe or wellbore tubular, comprising: pumping a solution or suspension containing at least one of carbon nanotubes (CNT) and CNT based derivatives into the pipe or wellbore tubular to a position proximate the solids; and applying at least one of electromagnetic energy and electric current at one or more selected frequencies to the pipe or wellbore tubular proximate the solution.
 2. The method of claim 1 wherein a frequency of the at least one of electromagnetic energy and electric current is 13.56 Megahertz.
 3. The method of claim 1 wherein a concentration of the carbon nanotubes and/or CNT based derivatives in the solution or suspension is in the range of 10 milligrams per liter to 90% by weight
 4. The method of claim 1 wherein the solids comprise at least one of hydrates, wax, asphaltenes and paraffins.
 5. A method for fusing solids in a subsea pipe or a wellbore tubular, comprising: coating a surface of the pipe or wellbore tubular with a material having carbon nanotubes (CNT) and/or CNT based derivatives suspended therein; and applying at least one of electromagnetic energy and electric current at one or more selected frequencies to a portion of the pipe or wellbore tubular having solids therein.
 6. The method of claim 5 wherein a frequency of the at least one of electromagnetic energy and electric current is 13.56 Megahertz.
 7. The method of claim 5 wherein the material comprises carbon nanotubes (CNT) and/or CNT based derivatives bonded directly to a surface of the pipe.
 8. The method of claim 5 wherein the solids comprise at least one of hydrates, wax, asphaltenes and paraffins. 